JP6290374B2 - EMM-25 molecular sieve material, its synthesis and use - Google Patents

Description

  The present invention relates to a novel molecular sieve material designated as EMM-25, its synthesis and its use as an adsorbent and / or hydrocarbon conversion catalyst.

  Molecular sieve materials, whether natural or synthesized, have so far proved useful as adsorbents and have catalytic properties for various hydrocarbon conversion reactions. Has been. Certain molecular sieves, such as zeolites, AlPO and mesoporous materials, are porous crystalline materials that have an ordered, well-defined crystal structure, as determined by X-ray diffraction (XRD). Within a crystalline molecular sieve material there are a number of vacancies that can be interconnected by a number of channels or pores. These pores and pores are uniform in diameter within a particular molecular sieve material. These pores are known as “molecular sieves” because they do not accept larger sized molecules, but accept certain sized adsorbed molecules, and are widely used in various industries. Used in the process.

Such molecular sieves, both natural and synthesized, contain a wide variety of positive ion-containing crystalline silicates. These silicates can be described as rigid three-dimensional frameworks of SiO ₄ tetrahedra and Group 13 element oxides of the periodic table (eg, AlO ₄ ). A tetrahedron is an electronic valence of a tetrahedron containing a group 13 element (eg, aluminum or boron) balanced by the inclusion of a cation, eg, a proton, alkali metal or alkaline earth metal cation, in the crystal. Cross-linking by sharing an oxygen atom with This is because the ratio of the number of group 13 elements (eg, aluminum or boron) to various cations, eg, H ⁺ , Ca ²⁺ / 2, Sr ²⁺ / 2, Na ⁺ , K ⁺ or Li ⁺ is equally matched. Can be represented.

Molecular sieves that find use in catalysis include either natural or synthetic crystalline molecular sieves. Examples of these molecular sieves include large pore zeolites, medium pore size zeolites and small pore zeolites. These zeolites and their isotypes are described in Non-Patent Document 1, which is incorporated herein by reference. Large pore zeolites generally have a pore size of at least about 6.5-7 angstroms and include LTL, MAZ, FAU, OFF, ^* BEA and MOR framework type zeolites (IUPAC Commission of Zeolite Nomenclature). Examples of large pore zeolites include mazzite, offretite, zeolite, zeolite Y, zeolite X, omega and beta. Medium pore size zeolites generally have a pore size of from about 4.5 angstroms to less than about 7 angstroms, for example MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW and TON framework types Zeolite is included (IUPAC Commission of Zeolite Nomenclature). Examples of medium pore size zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicate 1 and silicate 2. Small pore size zeolites have a pore size of about 3 Angstroms to less than about 5.0 Angstroms and include, for example, CHA, ERI, KFI, LEV, SOD and LTA framework type zeolites (IUPAC Commission of Zeolite Nomenclature). . Examples of small pore zeolites include ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabasite. , Zeolite T and ALPO-17.

“Atlas of Zeolite Framework Types”, Ch. Baerlocher, L.M. B. McCusker, D.C. H. Olson, Elsevier, 6th revised edition, 2007

  According to the present invention, the new zeolite structure shown as EMM-25 is: N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane-1,4-diammonium, N, N ′ -Dihexyl-N, N'-dipentyl-N, N'-dimethylbutane-1,4-diammonium, N, N, N ', N'-tetrapentyl-N, N'-dimethylbutane-1,4- Synthesis using at least one of the four organic templates of diammonium, N, N′-dipentyl-N, N′-dibutyl-N, N′-dimethylbutane-1,4-diammonium, and mixtures thereof It was done.

  In one aspect, the present invention relates to a molecular sieve material having, in its as-fired form, an X-ray diffraction pattern comprising the following peaks in Table 1.

  In another aspect, the present invention relates to a molecular sieve having a framework defined by the following connectivity for tetrahedral (T) atoms in the unit cell in Table 2. Tetrahedral atoms (T) are connected by bridging atoms.

Conveniently, the molecular sieve material can be such that n is at least 10 and X can be a trivalent element such as one or more of B, Al, Fe and Ga (especially containing B, Or B), and Y can be a tetravalent element such as one or more of Si, Ge, Sn, Ti and Zr (especially containing or being Si), X ₂ O ₃ : (n) It can have a composition comprising a molar relationship of YO ₂ .

  In another aspect, the invention relates to a molecular sieve material having, in its as-synthesized form, an X-ray diffraction pattern comprising the following peaks in Table 3.

Conveniently, the molecular sieve material is 0.004 <m / n ≦ 0.04, n can be at least 10, Q can be an organic structure directing agent, X is a trivalent element And can have a composition comprising a molar relationship of mQ: (n) YO ₂ : X ₂ O ₃ , wherein Y can be a tetravalent element.

  In one embodiment, X can be one or more of B, Al, Fe, Ga and Al, and Y can be one or more of Si, Ge, Sn, Ti and Zr.

Conveniently, Q is the following formula:
^{_{R 1 R 2 (CH 3)}} N + CH 2 CH 2 CH 2 CH 2 N + (CH 3) R 1 R 2
In which R ₁ and R ₂ can independently be selected from butyl, pentyl and hexyl.

Optionally, Q is N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane-1,4-diammonium (C ₄ diquat of dihexylmethylamine), N, N′-dihexyl. -N, N'-dipentyl -N, N'-dimethyl-butane-1,4-diammonium _{(C 4} diquat hexyl pentyl methylamine), N, N, N ' , N'- Tetorapenchiru -N, N' - _{(C 4} diquat of dipentyl methylamine) dimethylbutane-1,4-diammonium, N, N'-dipentyl -N, N'-dibutyl -N, N'-dimethyl-butane-1,4-diammonium (pentyl Or a cation selected from the group consisting of C ₄ diquat of butylmethylamine) and mixtures thereof.

In a further aspect, the invention is a method of manufacturing a molecular sieve material as described herein, wherein (i) preparing (or manufacturing) a synthetic mixture capable of forming the material. The mixture is water, hydroxide ion source, tetravalent element Y oxide source, trivalent element X source, optionally halide ion Z- source, optionally alkali Source of metal ion M ⁺ , as well as N, N, N ', N'-tetrahexyl-N, N'-dimethylbutane-1,4-diammonium cation, N, N'-dihexyl-N, N'- Dipentyl-N, N′-dimethylbutane-1,4-diammonium cation, N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium cation, N, N '-Dipentyl-N, Comprising a structure directing agent Q selected from the group consisting of '-dibutyl-N, N'-dimethylbutane-1,4-diammonium cation and mixtures thereof, and said synthetic mixture, in terms of molar ratio: Amount and / or range of:
YO ₂ / X ₂ O ₃ at least 2,
H ₂ O _/ YO ₂ 5~60,
OH ⁻ / YO ₂ 0.01 to 1,
Z ⁻ / YO _{2 0 to} 0.30,
M ⁺ / _YO 2 0~0.40, and Q _/ YO 2 0.03~1.0,
Having a composition of:
(Ii) heating the synthesis mixture at crystallization conditions comprising a temperature of about 100 ° C. to about 200 ° C. and a period of about 1 day to about 100 days until crystals of the material are formed; (iii) Recovering the crystalline material from the synthetic mixture.

Preferably, M ⁺ can include sodium and / or potassium ions, or can be sodium and / or potassium ions. When Z ⁻ is present, Z ⁻ can advantageously contain chloride ions or can be chloride ions.

Optionally, Q is N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium cation, N, N, N ′, N′-tetrahexyl-N , N′-dimethylbutane-1,4-diammonium cation and mixtures thereof. The structures of these cations are shown below.

  In another aspect, the present invention is a method for converting a raw material comprising an organic compound into a conversion product, wherein the raw material is subjected to organic compound conversion conditions, and the activated form of the molecular sieve material described herein. A method comprising the step of contacting with a catalyst comprising:

FIG. 1 shows the X-ray diffraction pattern of the synthesized zeolite of Example 1. FIG. 2 shows the X-ray diffraction pattern of a sample of the zeolite of Example 2 taken from the synthesis mixture: line a) about 17 days, line b) about 31 days, line c) about 38 days, line d) about 45 days and line e) about 52 days. FIG. 3 shows a scanning electron microscopy (SEM) image of the zeolite of Example 2 taken from the synthesis mixture at about 38 days. FIG. 4 shows the X-ray diffraction patterns of samples of the zeolite of Example 6 taken from the synthesis mixture at various periods: line a) about 25 days, line b) about 35 days and line c) about 49 days. FIG. 5 shows the X-ray diffraction patterns of the zeolite samples of Example 7 taken from the synthesis mixture at various time periods: line a) about 16 days, line b) about 23 days and line c) about 27 days. FIG. 6 shows the X-ray diffraction patterns of the zeolite samples of Example 8 taken from the synthesis mixture at various time periods: line a) about 7 days, line b) about 14 days and line c) about 21 days. FIG. 7 shows the X-ray diffraction patterns of the zeolite samples of Example 9 taken from the synthesis mixture at various time periods: line a) about 7 days, line b) about 21 days, line c) about 24 days and Line d) About 28 days.

  Described herein is a novel molecular sieve material designated as EMM-25, its synthesis in the presence of a structure directing agent, and its use as an adsorbent and hydrocarbon conversion catalyst.

  The new molecular sieve material EMM-25 can contain at least the peaks shown in Table 1 above in its as-baked form and at least the peaks shown in Table 3 above in its as-synthesized form. It can be characterized by a diffraction pattern.

  Optionally, the calcined form of the molecular sieve can have an XRD pattern that includes the additional peaks shown in Table 4 below.

  Optionally, the as-aligned form of the molecular sieve can have an XRD pattern that includes the additional peaks shown in Table 5 below.

  EMM-25 may additionally or alternatively be characterized by a framework defined by the connectivity of the tetrahedral (T) atoms shown in Table 2 above. Optionally, the tetrahedral atoms consist of Li, Be, Al, P, Si, Ga, Ge, Zn, Cr, Mg, Fe, Co, Ni, Mn, As, In, Sn, Sb, Ti and Zr. One or more elements selected from the group (eg, selected from the group consisting of Si, Ge, Sn, Ti, and Zr) may be included. Optionally, the bridging atom comprises one or more elements selected from the group consisting of O, N, F, S, Se and C. In such embodiments, the bridging atoms can preferably be predominantly oxygen atoms (eg, at least 90% of the bridging atoms may be oxygen).

  Optionally, the molecular sieve of the present invention can be borosilicate.

The X-ray diffraction data reported herein is a PANalytical X-Pert Pro diffraction system equipped with an X 'Celerator detector, using copper K-alpha radiation and a fixed 0.25 degree diverging slit. Collected. Diffraction data was recorded by a step scan of about 0.017 degrees 2-theta (Theta is a Bragg angle) and a count time of about 2 seconds for each step. The face (d−) spacing is calculated in angstroms, and the relative peak area intensity of the peak, I / I _(o) is an MDI Jade peak profile fitting algorithm to about 1/100 of the intensity of the strongest peak (above background) Was determined using. The peak intensity was not corrected for Lorentz and polarization effects. Diffraction data described for each sample as a single peak appears as a resolved (single local maximum) or partially resolved peak at certain conditions (such as differences in crystallographic changes) It should be understood that it may contain a number of overlapping peaks. Typically, such conditions (eg, crystallographic changes) can include slight changes in unit cell parameters and / or changes in crystal symmetry without corresponding changes in structure. These minor effects, including changes in relative strength, may additionally or alternatively include cation content, framework composition, nature and extent of pore packing, crystal size and shape, preferred orientation, heat and / or Or as a result of differences in hydrothermal history, etc., or combinations thereof.

The molecular sieve material (EMM-25), in its fired form, can have n of at least 10 (eg, about 10 to about 200) and X is a trivalent element (eg, B, Al, Fe and X ₂ O ₃ : (n) YO, which can be one or more of Ga) and Y can be a tetravalent element (eg, one or more of Si, Ge, Sn, Ti and Zr). It can have a chemical composition having a molar relationship of _two . In one preferred embodiment, X can comprise B or can be B and Y can comprise Si or can be Si.

The molecular sieve material (EMM-25) is, in its as-synthesized form, 0.004 <m / n ≦ 0.04, n can be at least 10, and Q is an organic structure directing agent. X can be a trivalent element (eg, one or more of B, Al, Fe and Ga) and Y can be a tetravalent element (eg, Si, Ge, Sn, Ti and Zr). Can have a chemical composition having a molar relationship of mQ: (n) YO ₂ : X ₂ O ₃ . Optionally, as in the fired form, X can comprise B, or can be B, and Y can comprise Si, or It can be Si.

  Suitable examples of organic structure directing agent Q include, but are not necessarily limited to, N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane-1,4-diammonium, N, N′— Dihexyl-N, N′-dipentyl-N, N′-dimethylbutane-1,4-diammonium, N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium Cations such as ammonium, N, N′-dipentyl-N, N′-dibutyl-N, N′-dimethylbutane-1,4-diammonium can be included.

  The Q component is typically associated with the as-synthesized form of the molecular sieve EMM-25 as a result of its presence during crystallization and is easily decomposed / removed by conventional post-crystallization methods such as calcination. Can be done.

  The molecular sieve material EMM-25 can advantageously represent a thermally stable zeolite with a unique XRD pattern.

EMM-25 has, water, a source of hydroxide ion, a source of an oxide of tetravalent element Y, a source of trivalent element X, halide ion Z optionally ^- a source of alkali and optionally It can be prepared from a synthetic mixture comprising a source of metal ions M ⁺ , eg sodium or potassium ions, and the directing agent Q described above. The synthesis mixture may have a composition relating to the molar ratio of oxides within the following amounts and / or ranges.

In the preferred embodiment there is, Z ^{- -} Z is, Cl ^- may be a ^- a comprise happens, or Cl. Additionally or alternatively, in preferred embodiments where M ⁺ is present, M ⁺ can comprise Na ⁺ and / or K ⁺ or can be Na ⁺ and / or K ^+. it can.

  A suitable source of tetravalent element Y may depend on the element Y selected (eg, silicon, germanium, strontium, titanium and zirconium). In embodiments where Y is silicon, suitable sources of silicon include colloidal suspensions of silica, precipitated silica, alkali metal silicates, tetraalkylorthosilicates, and fumed silica. In embodiments where Y is germanium, germanium oxide may be used as the oxide source.

  When present, a suitable source of the trivalent element X depends on the element X selected (eg, boron, aluminum, iron and gallium). In embodiments where X is boron, the source of boron comprises boric acid, sodium tetraborate and potassium tetraborate.

Q is preferably:
^{_{R 1 R 2 (CH 3)}} N + CH 2 CH 2 CH 2 CH 2 N + (CH 3) R 1 R 2
(Wherein R ₁ and R ₂ can be independently selected from butyl, pentyl and hexyl) or can be such cations.

  Nevertheless, suitable sources of directing agent Q can include, but are not necessarily limited to, hydroxides and / or salts of related quaternary ammonium compounds. N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane-1,4-diammonium compound includes, for example, dihexylmethylamine and 1,4-dihalobutane (for example, 1,4-diiodobutane). Alternatively, it can be easily synthesized by reaction with 1,4-dibromobutane). N, N′-dihexyl-N, N′-dipentyl-N, N′-dimethylbutane-1,4-diammonium compound includes, for example, hexylpentylmethylamine and 1,4-dihalobutane (for example, 1,4 It can be easily synthesized by reaction with diiodobutane or 1,4-dibromobutane). N, N, N ′, N′-tetrapentyl-N ′, N′-dimethylbutane-1,4-diammonium compound includes dipentylmethylamine and 1,4-dihalobutane (for example, 1,4-diiodobutane or 1,4-dibromobutane) can be easily synthesized. N, N′-dipentyl-N, N′-dibutyl-N, N′-dimethylbutane-1,4-diammonium compound includes pentylbutylmethylamine and 1,4-dihalobutane (for example, 1,4-diiodobutane). Alternatively, it can be easily synthesized by reaction with 1,4-dibromobutane).

  Crystallization of EMM-25 is performed in a suitable reactor vessel, such as a polypropylene jar, or a Teflon ™ lined or stainless steel autoclave, at about 100 ° C. to about 200 ° C. (eg, about 150 ° C. to about 170 ° C.). At a temperature sufficient for crystallization to occur at the temperature used (e.g., from about 1 day to about 100 days, from about 1 day to about 50 days, or from about 2 days to about 20 days), static or It can be carried out under stirring conditions. The synthesized crystals can then be separated from the liquid and advantageously recovered.

  The synthesis may be facilitated by seed crystals from a previous synthesis of EMM-25, where seed crystals, when present, are suitably from about 0.01 ppm by weight of the synthesis mixture to about 10,000 ppm by weight, for example, It constitutes an amount from about 100 ppm by weight to about 5000 ppm by weight.

Depending on the desired range and depending on the X ₂ O ₃ / YO ₂ molar ratio of the material, any cations of as-synthesized EMM-25 can be replaced according to well-known techniques by ion exchange with other cations. Can do. When utilized, preferred substituted cations can include metal ions, hydrogen ions, hydrogen precursor (eg, ammonium) ions, and mixtures thereof. When utilized, particularly preferred cations can include those capable of adjusting the catalytic activity for a particular hydrocarbon conversion reaction, such as hydrogen, rare earth elements and Group 2-15 metals of the Periodic Table of Elements. As used herein, the periodic table family numbering scheme is as disclosed in Chemical and Engineering News, 63 (5), 27 (1985).

  The molecular sieve described herein may be subjected to a treatment to remove some or all of the organic directing agent Q used in its synthesis. This can be conveniently performed by heat treatment (calcination), for example by heating the as-synthesized material to a temperature of at least about 370 ° C. for at least 1 minute (generally within 20 hours). Although pressures below atmospheric pressure can be utilized for heat treatment, atmospheric pressure can typically be desirable for reasons of convenience. The heat treatment can be performed at a temperature up to about 1000 ° C., for example, up to about 925 ° C. The heat treated product can be particularly useful in the catalysis of the conversion reaction of certain organics, such as hydrocarbons, especially in its metal, hydrogen and / or ammonium form.

  The molecular sieves described herein may be intimately combined with a hydrogenation component, eg, molybdenum, rhenium, nickel, cobalt, chromium, manganese or a noble metal (eg, platinum and / or palladium) Treatment-dehydrogenation may be desired. Such components are intimately physically mixed with it by impregnation therein, by being exchanged into the composition (to the extent that the Group 13 element, eg, aluminum is in the structure) Or the like, or some combination thereof, can be present in the composition as co-crystallization. Such components can be impregnated in / on the molecular sieve, for example in the case of platinum, by treating the silicate with a solution containing platinum metal-containing ions. Thus, suitable platinum compounds for this purpose can include, but are not necessarily limited to, chloroplatinic acid, primary platinum chloride, various compounds containing platinum amine complexes, or mixtures / combinations thereof. .

  The molecular sieve of the present disclosure is suitable for use as an adsorbent or catalyst, for example, in an atmosphere (containing air, nitrogen, etc.), at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure. By heating to a temperature of about 100 ° C. to about 500 ° C. (eg, about 200 ° C. to about 370 ° C.) for a time, eg, about 30 minutes to about 48 hours, advantageously at least partially (or substantially ) Can be dehydrated. Dehydration can additionally or alternatively be performed at room temperature (approximately 20-25 ° C.), for example, simply by placing EMM-25 under vacuum (eg, 0.01 Torr or less). However, longer time may be required to fully dehydrate.

  The molecular sieves of the present disclosure are used as adsorbents or as catalysts for a wide variety of organic compound conversion processes, including many of the current commercial / industrial importance, especially in its borosilicate form. May be. Examples of chemical transformation processes in which the crystalline material of the present invention can be effectively catalyzed by itself or in combination with one or more other catalytically active materials (including other crystalline catalysts) And those requiring a catalyst having acid activity. Examples of organic conversion processes that EMM-25 can catalyze include, but are not necessarily limited to, (hydro) cracking, disproportionation, alkylation, isomerization / dewaxing, and the like, and combinations thereof.

  As with many catalysts, it may be desirable to combine EMM-25 with another component that is resistant to the temperatures and other conditions utilized in the organic conversion process. Such components can include active and inert materials, synthetic or natural zeolites, and inorganic materials such as clays, silica and / or metal oxides such as alumina. The latter may be of natural origin, in the form of a gelatinous precipitate, or in the form of a gel comprising a mixture of silica and other metal oxides. Using the material with EMM-25 (ie, existing during the synthesis of the crystalline material that can be combined with it or in its active state) can cause the level of conversion and There may be a tendency to change the selectivity of the catalyst. The inert material suitably utilizes, for example, other means to control the amount of conversion in a given process and to control the rate of reaction of the product in an economical and orderly manner, for example. It can serve as a diluent so that it can be obtained. These materials may be incorporated into naturally derived clays, such as bentonite and / or kaolin, to improve the crushing strength of the catalyst under commercial operating conditions. The above materials, ie clays, oxides, etc. can act as binders for the catalyst. It would be desirable to provide a catalyst with good crush strength because it may be desirable to prevent / limit the catalyst from grinding into powder-like materials (fine particles) in commercial use. Can do. For example, these clay and / or oxide binders can only be utilized to improve the crush strength of the catalyst.

  Naturally derived clays that can be combined with EMM-25 can include the montmorillonite and kaolin families, including subbentonites, which are generally diixie, McNamee, Georgia and Florida clays, and the main mineral components are halloysite, kaori. Known as knight, dickite, nacrite or other anarchite. Such clays can be used in the raw state (as originally mined) and / or initially subjected to calcination, acid treatment and / or chemical modification. Binders useful for combination with EMM-25 can additionally or alternatively include inorganic oxides such as silica, zirconia, titania, magnesia, beryllia, alumina and mixtures thereof.

  In addition to or instead of the above materials, as desired, EMM-25 is a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania. , And ternary compositions such as silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, and mixtures or combinations thereof.

  The relative proportions of EMM-25 and inorganic oxide matrix may vary widely, and the EMM-25 content is typically about 1% to about 90% by weight, or in particular, the composite is beaded. In the form of about 2 wt% to about 80 wt% based on the total composite weight.

  The invention can include one or more of the following embodiments in addition or as an alternative.

Embodiment 1. FIG. A molecular sieve material having an X-ray diffraction pattern comprising the peaks listed in Table 1 in a fired form.

Embodiment 2. FIG. A molecular sieve material having a framework defined by connectivity with respect to tetrahedral (T) atoms in the unit cell shown in Table 2, wherein the tetrahedral atoms (T) are connected by bridging atoms.

Embodiment 3. FIG. n is at least 10, X is a trivalent element (eg, comprises one or more of B, Al, Fe and Ga, eg, comprises or is B) and Y There is a tetravalent element (e.g., comprise Si, Ge, Sn, one or more of Ti and Zr, e.g., comprise Si, or _{Si), (n) YO 2} : X 2 The molecular sieve material of embodiment 1 or embodiment 2 having a composition comprising a molar relationship of O ₃ .

Embodiment 4 FIG. The molecular sieve material of embodiment 3 further comprising a noble metal and / or a salt of the noble metal.

Embodiment 5. FIG. A molecular sieve material having an X-ray diffraction pattern including the peaks described in Table 3 in the as-synthesized form.

Embodiment 6. 0.004 <m / n ≦ 0.04, n is at least 10, Q is an organic structure directing agent, and X is a trivalent element (eg, B, Al, Fe and Ga) Comprising one or more, for example comprising B or B, and Y comprising one or more of tetravalent elements (for example Si, Ge, Sn, Ti and Zr). The molecular sieve material of embodiment 5 having a composition comprising a molar relationship of mQ: (n) YO ₂ : X ₂ O ₃ , eg comprising or being Si).

Embodiment 7. FIG. Q is represented by the following formula: R ₁ R ₂ (CH ₃ ) N ⁺ CH ₂ CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) R ₁ R ₂ , wherein R ₁ and R ₂ are independently butyl, Q is selected from pentyl and hexyl (eg, Q is N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane-1,4-diammonium, N, N ′ -Dihexyl-N, N'-dipentyl-N, N'-dimethylbutane-1,4-diammonium, N, N, N ', N'-tetrapentyl-N, N'-dimethylbutane-1,4- A cation selected from the group consisting of diammonium, N, N′-dipentyl-N, N′-dibutyl-N, N′-dimethylbutane-1,4-diammonium, and mixtures thereof), embodiments 6 molecular sieve materials.

Embodiment 8. FIG. It is a manufacturing method of the molecular sieve material in any one of Embodiments 1-7, Comprising: It is the step which prepares (or manufactures) the synthetic mixture which can form the said material, but the said mixture is water. , Hydroxide ion source, tetravalent element Y oxide source, trivalent element X source, optionally halide ion Z ⁻ source, optionally alkali metal ion M ⁺ source Source, and N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane-1,4-diammonium cation, N, N′-dihexyl-N, N′-dipentyl-N, N ′ -Dimethylbutane-1,4-diammonium cation, N, N, N ', N'-tetrapentyl-N, N'-dimethylbutane-1,4-diammonium cation, N, N'-dipentyl-N, N'-dibutyl-N, N'-di Comprising a structure directing agent Q selected from the group consisting of tilbutane-1,4-diammonium cation and mixtures thereof, and said synthetic mixture, in terms of molar ratio, has the following amount and / or range; YO ₂ / X ₂ O ₃ , 5 to 60 H ₂ O / YO ₂ , 0.01 to 1 OH ⁻ / YO ₂ , 0 to 0.30 Z ⁻ / YO ₂ , 0.03 to 1.0 Having a composition of Q / YO ₂ of 0 and M ⁺ / YO ₂ of ^{0 to} 0.40; and (ii) a temperature of about 100 ° C. to about 200 ° C. and about 1 until crystals of the material are formed. Heating the synthesis mixture at crystallization conditions comprising a period of from about 100 days to about 100 days; and (iii) recovering the crystalline material from the synthesis mixture.

Embodiment 9. FIG. Embodiment 9. The method of embodiment 8 wherein the source of trivalent element X is boric acid, sodium tetraborate and potassium tetraborate.

Embodiment 10 FIG. The method of embodiment 8 or embodiment 9, wherein the synthesis mixture has a pH of 8.0 to 10.5.

Embodiment 11. FIG. A method for converting a raw material comprising an organic compound into a conversion product, wherein the raw material is subjected to organic compound conversion conditions, and any of Embodiments 1-7 and / or any of Embodiments 8-10 Contacting with a catalyst comprising an active form of the molecular sieve material produced according to the above.

  The invention may be described with particular reference to the following non-limiting examples and the accompanying drawings.

Example 1
First, within about 23 mL of a steel Parr autoclave Teflon ™ liner, dihexylmethylamine C ₄ diquat (N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane-1, 4-diammonium hydroxide; [OH] ≈0.59 mmol / g) about 5.08 g hydroxide solution was mixed with about 2.22 g deionized water. Next, about 0.19 g of boric acid was added to the solution and mixed until almost completely dissolved. Then about 2.25 g Ludox ™ AS-40 (a colloidal suspension of about 40 wt% silica in water) is added to the solution, about 1.50 g of 1N HCl is added and mixed, A relatively uniform suspension was made. The synthesis mixture had the following molar ratios: Si: B≈5; HCl: Si≈0.10; H 2 O: Si≈35; and Q: Si≈0.1. The liner was then coated and the interior of the approximately 23 mL autoclave was sealed and heated at approximately 160 ° C. under tumbling conditions (approximately 40 rpm). After about 38 days, the reactor was removed and quenched, then the solid was isolated by filtration, washed, dried and analyzed using powder XRD. FIG. 1 shows that the product powder XRD appeared to be a mixture of amorphous material and EMM-25.

Example 2
Example 1 was repeated using seed crystals of the EMM-25 product from Example 1 (approximately 0.04 g seed crystals / 1 g SiO 2). The reactor was removed and quenched after various heating periods. An aliquot of the gel mixture was removed and the solid was isolated by filtration, washed, dried and then analyzed using powder XRD. FIG. 2 shows that after about 38 days of heating, the synthesis appeared to be almost complete, and after about 52 days of heating, it appeared to be completely complete. The powder XRD pattern of the final product was able to show C-centered orthorhombic crystals (a≈22.95ｂ, b≈11.07Å, c≈24.85Å). FIG. 3 shows an SEM image of the product collected after about 38 days. The product appeared to have a few amorphous phases but mostly a crystalline phase. This image appeared to show a crystal plate having an edge from about 0.25 microns to about 1 micron in length and a thickness from about 0.025 microns to about 0.1 microns.

  The final product from Example 2 was heated in a muffle furnace from ambient temperature (about 20-25 ° C.) to about 400 ° C. at about 4 ° C./min under a nitrogen atmosphere and then in air at about 4 ° C./minute. Heated to about 600 ° C. in minutes and maintained at about 600 ° C. in air for about 2 hours. The calcined product was then measured by nitrogen physisorption and Lippens, B .; C. And deBoer, J .; H. , “Studies on pore systems in catalysts: V. Catal. , 4, 319 (1965), data were analyzed by t-plot method. The determined micropore volume was about 0.15 cm 3 / g and the total BET surface area was about 419 m 2 / g.

Example 3 Synthesis of N, N, N ′, N′-Tetrahexyl-N, N′-dimethylbutane-1,4-diammonium hydroxide Diquaternary of N, N-dihexyl-N-methylamine The ammonium salt was prepared by reaction with 1,4-dibromobutane. About 25.0 g N, N-dihexyl-N-methylamine (Aldrich, about 0.125 mol) and about 12.3 g 1,4-dibromobutane in about 100 mL acetone in about 500 mL round bottom flask (About 0.057 mol) was added. The resulting mixture was then refluxed for about 2 days. The solution was then removed by rotary evaporation and the product oil was extracted with ether to remove unreacted amine. The oil was then dried by rotary evaporation at about 80 ° C. with gradually decreasing pressure (up to about 50 torr). The dibromide product was then ion exchanged to the hydroxide form by dissolving in a mixture of water and ethanol. To this solution, an approximately 2-fold excess of Dowex ™ LC NG hydroxide exchange resin was added. The solution was collected by resin filtration and extensive washing. The hydroxide solution was then extracted with ether to remove any amine impurities and then concentrated by rotary evaporation at about 65 ° C. with gradually decreasing pressure (up to about 50 torr). The concentration of the aqueous solution was determined by titration using a standard solution of about 0.1 N HCl.

Ｎ−ペンチル−Ｎ−ヘキシル−Ｎ−メチルアミンは、Ｎ−ヘキシル−Ｎ−メチルアミンによるバレルアルデヒド（Ｎ−ペンタナール）の還元アミノ化によって調製した。約５００ｍＬのテトラヒドロフラン（ＴＨＦ）を約１Ｌの吸引力フラスコに配置した。約２８．４ｇのバレルアルデヒド（約０．３４モル）と、次いで、約３７．８ｇのＮ−ヘキシル−Ｎ−メチルアミン（約０．３３モル）をＴＨＦ中に混合した。約１００ｇのナトリウムトリアセトキシボロヒドリド粉末を、次いで、約５〜１０ｇ増加で溶液に添加した。添加の間、強力な撹拌を使用して、確実に、可能な限り少ない粉末がフラスコの底部に凝集するようにし、それによって懸濁液の効率的な混合を防いだ。ナトリウムトリアセトキシボロヒドリド粉末のそれぞれの添加の後、粉末の次の添加の前に比較的均一なスラリーを形成するために適切な時間が提供された。全ての粉末が添加されたら、次いで、窒素フローを実行した。一晩の混合（約８〜１６時間）後、約２７５ｇの約２４質量％のＫＯＨ（水）溶液をゆっくり添加することによって懸濁液をクエンチして、生成物を仕上げた。次いで、ペンタンを用いて、得られた溶液から生成物を抽出した。次いで、有機フラクションを分液漏斗で収集し、無水硫酸マグネシウムを用いて乾燥させた。次いで、徐々に圧力を低下させて（約５０トルまで）、ＴＨＦおよびペンタン溶媒の回転式蒸発によってアミン生成物を単離し、約６０．６ｇのアミン生成物（^１Ｈ ＮＭＲによると純度約９５％）が得られた。 Example 4 Synthesis of N, N′-dihexyl-N, N′-dipentyl-N, N′-dimethylbutane-1,4-diammonium hydroxide

N-pentyl-N-hexyl-N-methylamine was prepared by reductive amination of valeraldehyde (N-pentanal) with N-hexyl-N-methylamine. About 500 mL of tetrahydrofuran (THF) was placed in an about 1 L suction flask. About 28.4 g valeraldehyde (about 0.34 mol) and then about 37.8 g N-hexyl-N-methylamine (about 0.33 mol) were mixed in THF. About 100 g of sodium triacetoxyborohydride powder was then added to the solution in about 5-10 g increments. During the addition, strong agitation was used to ensure that as little powder as possible aggregated at the bottom of the flask, thereby preventing efficient mixing of the suspension. After each addition of sodium triacetoxyborohydride powder, adequate time was provided to form a relatively uniform slurry before the next addition of powder. Once all the powder was added, a nitrogen flow was then performed. After overnight mixing (about 8-16 hours), the product was finished by quenching the suspension by slowly adding about 275 g of about 24 wt% KOH (water) solution. The product was then extracted from the resulting solution using pentane. The organic fraction was then collected on a separatory funnel and dried using anhydrous magnesium sulfate. The pressure was then gradually reduced (up to about 50 torr) and the amine product was isolated by rotary evaporation of THF and pentane solvent to give about 60.6 g of amine product (purity about 95% according to ¹ H NMR). )was gotten.

  The diquaternary ammonium salt of N-pentyl-N-hexyl-N-methylamine was prepared by reaction with 1,4-dibromobutane. About 60.6 g N-pentyl-N-hexyl-N-methylamine (about 0.32 mol) and about 31.9 g 1,4-dibromobutane in about 150 mL acetone in about 500 mL round bottom flask (About 0.15 mol) was added. The resulting mixture was then refluxed for about 2 days. The solution was then removed by rotary evaporation and the product oil was extracted with ether to remove unreacted amine. The oil was then gradually reduced in pressure (up to about 50 torr) at about 80 ° C. and dried by rotary evaporation to give about 84.1 g of product. The dibromide product was then ion exchanged to the hydroxide form by dissolving in water and adding an approximately 2-fold excess of Dowex ™ LC NG hydroxide exchange resin. The solution was then recovered by resin filtration and extensive washing. The aqueous solution was then concentrated by rotary evaporation of water at about 65 ° C. with gradually decreasing pressure (up to about 50 torr). The concentration of the aqueous solution was determined by titration using a standard solution of about 0.1 N HCl.

ジ−Ｎ−ペンチル−Ｎ−メチルアミンは、実施例４の手順と同様の手順を使用することによって、ジ−Ｎ−ペンチルアミンによるホルムアルデヒドの還元アミノ化によって調製した。ジ−Ｎ−ペンチル−Ｎ−メチルアミンのジ第４級アンモニウム塩は、実施例４に記載の手順と同様の手順を使用することによって、１，４−ジブロモブタンとの反応によって調製した。 Example 5 Synthesis of N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium hydroxide

Di-N-pentyl-N-methylamine was prepared by reductive amination of formaldehyde with di-N-pentylamine by using a procedure similar to that of Example 4. The diquaternary ammonium salt of di-N-pentyl-N-methylamine was prepared by reaction with 1,4-dibromobutane by using a procedure similar to that described in Example 4.

Example 6
About 23 mL of steel Parr autoclave Teflon ™ liner inside N, N′-dihexyl-N, N′-dipentyl-N, N′-dimethylbutane-1,4-diammonium hydroxide (N-hexyl) About 3.84 g hydroxide solution of N-pentyl-N methylamine C ₄ diquat; [OH] ≈0.78 mmol / g) was mixed with about 3.42 g of deionized water. Next, about 0.19 g of boric acid was added to the solution and mixed until almost completely dissolved. About 2.25 g Ludox ™ AS-40 was then added to the solution, about 1.50 g 1N HCl was added and mixed to create a relatively uniform suspension. EMM-25 seed crystals (about 0.04 g) were added to the suspension. The liner was then coated and the interior of the approximately 23 mL autoclave was sealed and heated at approximately 160 ° C. under tumbling conditions (approximately 40 rpm). The reactor was removed after about 25 days, about 35 days, and about 49 days of heating, quenched, and a small sample of product was taken. FIG. 4 shows that EMM-25 appeared to be slowly crystallizing after appearing to be incomplete after about 49 days.

Example 7
Within about 23 mL of steel Parf autoclave Teflon ™ liner, N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium hydroxide (di-N— _{C 4} diquat pentyl -N- methylamine; [OH] hydroxide solution ≒ 0.68 mmol / g) to about 4.41 g, was mixed with deionized water to about 2.81 g. Next, about 0.19 g of boric acid was added to the solution and mixed until almost completely dissolved. About 2.25 g Ludox ™ AS-40 was then added to the mixture, about 1.50 g 1N HCl was added and mixed to create a relatively uniform suspension. EMM-25 seed crystals (about 0.04 g) were added to the suspension. The liner was then coated and the interior of the approximately 23 mL autoclave was sealed and heated at approximately 160 ° C. under tumbling conditions (approximately 40 rpm). After about 16 days, about 23 days, and about 27 days of heating, the reactor was removed, quenched, and a small sample of product was taken. FIG. 5 shows that EMM-25 appeared to be almost completely crystallized after about 27 days.

Example 8
Example 7 was repeated except that a ratio of NaOH / Si≈0.04 was used. In Example 8, N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium hydroxide inside about 23 mL of a steel Parr autoclave Teflon ™ liner. About 4.40 g of a hydroxide solution of (di-N-pentyl-N-methylamine C ₄ diquat; [OH] ≈0.68 mmol / g) was mixed with about 2.24 g of deionized water. To this solution was added about 0.60 g of about 1N NaOH. Next, about 0.19 g of boric acid was added to the solution and mixed until almost completely dissolved. About 2.25 g Ludox ™ AS-40 was then added to the mixture, about 1.50 g 1N HCl was added and mixed to create a relatively uniform suspension. EMM-25 seed crystals (about 0.04 g) were added to the suspension. The liner was then coated and the interior of the approximately 23 mL autoclave was sealed and heated at approximately 160 ° C. under tumbling conditions (approximately 40 rpm). The reactor was removed after about 7 days, about 14 days, and about 21 days of heating, quenched, and a small sample of product was taken. FIG. 6 shows that EMM-25 appeared to be fully crystallized after about 21 days.

Example 9
Example 7 was repeated except that the liner was heated at about 170 ° C. instead of about 160 ° C. After about 7 days, about 21 days, about 24 days, and about 28 days of heating, the reactor was removed, quenched, and a small sample of product was taken. FIG. 7 shows that EMM-25 appeared to crystallize completely or nearly completely after about 28 days.

Example 10
Example 7 was repeated except that no HCl was added to the reaction. Within about 23 mL of steel Parf autoclave Teflon ™ liner, N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium hydroxide (di-N— _{C 4} diquat pentyl -N- methylamine; [OH] hydroxide solution ≒ 0.68 mmol / g) to about 4.41 g, was mixed with deionized water to about 4.27 g. Next, about 0.19 g of boric acid was added to the solution and mixed until almost completely dissolved. About 2.25 g Ludox ™ AS-40 was then added to the mixture and mixed to create a relatively uniform suspension. EMM-25 seed crystals (about 0.04 g) were added to the suspension. The liner was then coated and the interior of the approximately 23 mL autoclave was sealed and heated at approximately 160 ° C. under tumbling conditions (approximately 40 rpm). After about 27 days of heating, the product appeared to be fully crystallized EMM-25 with trace impurities of ZSM-5.

Example 11
Within about 23 mL of steel Parf autoclave Teflon ™ liner, N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium hydroxide (di-N— About 2.63 g hydroxide solution of C ₄ diquat of pentyl-N-methylamine; [OH] ≈0.68 mmol / g) and about 0.72 g of about 1 N NaOH, about 5.20 g of deionized water. Mixed with. Next, about 0.093 g of boric acid was dissolved in the solution. About 0.54 g of Cabosil ™ M-5 fumed silica was then added to the mixture and mixed to create a relatively uniform suspension. EMM-25 seed crystals (about 0.04 g) were added to the suspension. The liner was then coated and the interior of the approximately 23 mL autoclave was sealed and heated at approximately 160 ° C. under tumbling conditions (approximately 40 rpm). After about 7 days of heating, the product appeared to be fully crystallized EMM-25 with trace impurities of ZSM-5.

Example 12
Example 11 was repeated except that about 1N KOH was used instead of about 1N NaOH. After about 7 days of heating, the product appeared to be fully crystallized EMM-25 with trace impurities of ZSM-5.

Example 13
The same reaction as Example 11 was repeated except that alkali hydroxide was not used in the reaction. Within about 23 mL of steel Parf autoclave Teflon ™ liner, N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium hydroxide (di-N— About 3.69 g hydroxide solution of pentyl-N-methylamine C ₄ diquat; [OH] ≈0.68 mmol / g) was mixed with about 7.93 g deionized water. Next, about 0.13 g of boric acid was dissolved in the solution. About 0.76 g of Cabosil ™ M-5 fumed silica was then added to the mixture and mixed to create a relatively uniform suspension. EMM-25 seed crystals (about 0.04 g) were added to the suspension. The liner was then coated and the interior of the approximately 23 mL autoclave was sealed and heated at approximately 160 ° C. under tumbling conditions (approximately 40 rpm). After about 13 days of heating, the product was determined to be substantially pure EMM-25.

Example 14
Example 12 was repeated using half the amount of about 1N KOH. Within about 23 mL of steel Parf autoclave Teflon ™ liner, N, N, N ′, N′-tetrapentyl-N, N′-dimethylbutane-1,4-diammonium hydroxide (di-N— Ptyl-N-methylamine C ₄ diquat; [OH] ≈0.68 mmol / g) about 2.63 g hydroxide solution, about 5.55 g deionized water and about 0.36 g about 1 N KOH Mixed with. Next, about 0.093 g of boric acid was dissolved in the solution. Approximately 0.54 g of Cabosil ™ M-5 fumed silica was then added to the mixture and mixed to create a uniform suspension. EMM-25 seed crystals (about 0.04 g) were added to the suspension. The liner was then coated and the interior of the approximately 23 mL autoclave was sealed and heated at approximately 160 ° C. under tumbling conditions (approximately 40 rpm). After about 10 days of heating, the product was determined to be EMM-25 with trace amounts of ZSM-5 impurities.

Example 15
Example 14 was repeated except that the liner was heated at about 175 ° C. instead of about 160 ° C. After about 11 days of heating, the product of Example 14 was determined to be EMM-25 with trace amounts of layered phase impurities.

Characterization The as-synthesized sample of EMM-25 produced an XRD pattern with the following peaks (these values are approximate):

  The as-synthesized EMM-25 is heated from ambient temperature (about 20-25 ° C.) to about 400 ° C. in a muffle furnace in a stream of nitrogen in about 2 hours and maintained at this temperature for about 15 minutes, The gas flow is switched to air, the temperature is increased from about 400 ° C. to about 600 ° C. in about 2 hours, maintained at a temperature of about 600 ° C. for about 2 hours, and then the furnace is brought to ambient temperature (about 20-25 ° C.) Calcination by cooling to. The as-fired sample of EMM-25 yielded an XRD pattern with the following peaks (these values are approximate):

A sample of as-fired EMM-25 was further tested for its ability to adsorb n-hexane, 2,2-dimethylbutane and mesitylene. All materials are thermally treated at about 500 ° C. for a time sufficient to substantially dehydrate the materials and / or remove any adsorbed species before performing the adsorption test. The hydrocarbon was then introduced through a super jar to saturate the nitrogen stream. Each adsorbate was adsorbed at different temperatures: hexane at about 90 ° C, 2,2-dimethylbutane at about 120 ° C, and mesitylene at 100 ° C. The results are summarized below.
n-Hexane About 80.6mg / g
2,2-dimethylbutane approx. 51.3 mg / g
Mesitylene about 22.2 mg / g

A sample of as-synthesized EMM-25 was also analyzed for boron content by ¹² B NMR using signal intensity comparisons with known boron concentration standards. The boron concentration of EMM-25 was found to be about 0.63% by weight.

Although the invention has been described and illustrated with reference to specific embodiments, those skilled in the art will recognize that the invention is not necessarily related to the variations illustrated herein. For this reason, reference should only be made to the appended claims for purposes of determining the true scope of the present invention.
The disclosure of the present specification may include the following aspects.
(Aspect 1)
A molecular sieve material having an X-ray diffraction pattern comprising the peaks listed in Table 1 in a fired form.
(Aspect 2)
A molecular sieve material having a framework defined by connectivity for tetrahedral (T) atoms in the unit cell described in Table 2, wherein the molecular sieve is connected by bridging atoms. material.
(Aspect 3)
n is at least 10, X is a trivalent element (eg, includes one or more of B, Al, Fe, and Ga, eg, includes or is B), and Y is a tetravalent element A composition comprising a molar relationship of (n) YO ₂ : X ₂ O ₃ that is (eg, includes one or more of Si, Ge, Sn, Ti, and Zr, eg, includes Si or is Si). The molecular sieve material according to aspect 1 or aspect 2 having:
(Aspect 4)
The molecular sieve material according to embodiment 3, further comprising a noble metal and / or a salt of the noble metal.
(Aspect 5)
A molecular sieve material having an X-ray diffraction pattern including the peaks described in Table 3 in the as-synthesized form.
(Aspect 6)
0.004 <m / n ≦ 0.04, n is at least 10, Q is an organic structure directing agent, X is a trivalent element (for example, one or more of B, Al, Fe and Ga) Including, for example, B or B, and Y includes one or more of tetravalent elements (for example, Si, Ge, Sn, Ti and Zr, for example, including Si, or The molecular sieve material according to aspect 5, having a composition comprising a molar relationship of mQ: (n) YO ₂ : X ₂ O ₃ , which is Si) .
(Aspect 7)
Q is represented by the following formula: R ₁ R ₂ (CH ₃ ) N ⁺ CH ₂ CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) R ₁ R ₂ , wherein R ₁ and R ₂ are independently butyl, Q is selected from pentyl and hexyl (eg, Q is N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane-1,4-diammonium, N, N ′ -Dihexyl-N, N'-dipentyl-N, N'-dimethylbutane-1,4-diammonium, N, N, N ', N'-tetrapentyl-N, N'-dimethylbutane-1,4- A cation selected from the group consisting of diammonium, N, N′-dipentyl-N, N′-dibutyl-N, N′-dimethylbutane-1,4-diammonium, and mixtures thereof), embodiment 6 The molecular sieve material described in 1.
(Aspect 8)
A method for producing a molecular sieve material according to any one of aspects 1 to 7,
(I) preparing a synthetic mixture capable of forming the material, wherein the mixture comprises water, a hydroxide ion source, a tetravalent element Y oxide source, a trivalent element; A source of X, optionally a source of halide ions Z ⁻ , optionally a source of alkali metal ions M ⁺ , and N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane -1,4-diammonium cation, N, N′-dihexyl-N, N′-dipentyl-N, N′-dimethylbutane-1,4-diammonium cation, N, N, N ′, N′-tetra Pentyl-N, N′-dimethylbutane-1,4-diammonium cation, N, N′-dipentyl-N, N′-dibutyl-N, N′-dimethylbutane-1,4-diammonium cation and their Selected from the group consisting of mixtures Is comprise becomes a structure directing agent Q is and the synthetic mixture, with respect to the molar ratio, the following amounts and / or range: at least one _{YO 2 / X 2 O 3,} 5~60 of _H 2 O / YO ₂ , 0.01-1 OH ⁻ / YO ₂ , 0 −0.30 Z ⁻ / YO ₂ , 0.03 to 1.0 Q / YO ₂ , and 0 to 0.40 M ⁺ / YO _2. Having a composition of:
(Ii) heating the synthesis mixture at crystallization conditions comprising a temperature of about 100 ° C. to about 200 ° C. and a period of about 1 day to about 100 days until crystals of the material are formed; and
(Iii) recovering the crystalline material from the synthesis mixture
Including methods.
(Aspect 9)
The method according to aspect 8, wherein the source of the trivalent element X is one or more of boric acid, sodium tetraborate, and potassium tetraborate.
(Aspect 10)
10. A method according to aspect 8 or 9, wherein the synthesis mixture has a pH of 8.0 to 10.5.
(Aspect 11)
A method for converting a raw material containing an organic compound into a conversion product, wherein the raw material is subjected to organic compound conversion conditions, according to any one of aspects 1 to 7 and / or according to any one of aspects 8 to 10. Contacting with a catalyst comprising an active form of the molecular sieve material produced according to the method.

Claims (11)

A calcined form, the following peaks (d-spacing (Å) / relative intensity (%)):
11.74-11.34 / 60-100,
9.50-9.10 / 30-80,
8.68-8.28 / 10-40,
5.64-5.44 / 20-60,
4.52 to 4.42 / 10-50,
4.28-4.18 / 10-40,
3.96-3.86 / 40-80, and
3.69 to 3.59 / 30 to 70
A borosilicate molecular sieve material having an X-ray diffraction pattern. A borosilicate molecular sieve material having a framework that is defined by the coupling with respect to the tetrahedral (T) atoms in the single-position grid, rag the tetrahedral atoms (T) are connected by a bridging atom, as follows Silicate molecular sieve material ,
T1 atom is connected to T3, T4, T33, T71 atoms,
T2 atom is connected to T5, T48, T72, T82 atoms,
T3 atom is connected to T1, T31, T47, T97 atoms,
T4 atoms are connected to T1, T5, T81, T106 atoms,
T5 atom is connected to T2, T4, T55, T75 atoms,
T6 atom is connected to T8, T9, T38, T76 atom,
T7 atom is connected to T10, T43, T77, T84 atoms,
T8 atoms are connected to T6, T36, T42, T98 atoms,
T9 atom is connected to T6, T10, T83, T105 atoms,
T10 atoms are connected to T7, T9, T60, T80 atoms,
T11 atom is connected to T13, T14, T23, T61 atoms,
T12 atoms are connected to T15, T58, T62, T86 atoms,
T13 atom is connected to T11, T21, T57, T99 atoms,
T14 atoms are connected to T11, T15, T85, T108 atoms,
T15 atoms are connected to T12, T14, T45, T65 atoms,
T16 atoms are connected to T18, T19, T28, T66 atoms,
T17 atom is connected to T20, T53, T67, T88 atoms,
T18 atoms are connected to T16, T26, T52, T100 atoms,
T19 atom is connected to T16, T20, T87, T107 atoms,
T20 atoms are connected to T17, T19, T50, T70 atoms,
T21 atom is connected to T13, T23, T24, T51 atoms,
T22 atoms are connected to T25, T52, T68, T90 atoms,
T23 atom is connected to T11, T21, T67, T101 atoms,
T24 atoms are connected to T21, T25, T89, T110 atoms,
T25 atoms are connected to T22, T24, T55, T75 atoms,
T26 atoms are connected to T18, T28, T29, T56 atoms,
T27 atom is connected to T30, T57, T63, T92 atoms,
T28 atom is connected to T16, T26, T62, T102 atoms,
T29 atom is connected to T26, T30, T91, 109 atom,
T30 atoms are connected to T27, T29, T60, T80 atoms,
T31 atom is connected to T3, T33, T34, T41 atoms,
T32 atoms are connected to T35, T42, T78, T94 atoms,
T33 atoms are connected to T1, T31, T77, T103 atoms,
T34 atoms are connected to T31, T35, T93, T112 atoms,
T35 atoms are connected to T32, T34, T45, T65 atoms,
T36 atoms are connected to T8, T38, T39, T46 atoms,
T37 atoms are connected to T40, T47, T73, T96 atoms,
T38 atom is connected to T6, T36, T72, T104 atoms,
T39 atom is connected to T36, T40, T95, T111 atoms,
T40 atoms are connected to T37, T39, T50, T70 atoms,
T41 atom is connected to T31, T43, T44, T73 atoms,
T42 atoms are connected to T8, T32, T45, T86 atoms,
T43 atom is connected to T7, T41, T71, T103 atoms,
T44 atoms are connected to T41, T45, T85, T112 atoms,
T45 atoms are connected to T15, T35, T42, T44 atoms,
T46 atom is connected to T36, T48, T49, T78 atom,
T47 atoms are connected to T3, T37, T50, T88 atoms,
T48 atoms are connected to T2, T46, T76, T104 atoms,
T49 atom is connected to T46, T50, T87, T111 atoms,
T50 atoms are connected to T20, T40, T47, T49 atoms,
T51 atom is connected to T21, T53, T54, T63 atom,
T52 atom is connected to T18, T22, T55, T82 atoms,
T53 atom is connected to T17, T51, T61, T101 atoms,
T54 atoms are connected to T51, T55, T81, T110 atoms,
T55 atom is connected to T5, T25, T52, T54 atoms,
T56 atoms are connected to T26, T58, T59, T68 atoms,
T57 atom is connected to T13, T27, T60, T84 atoms,
T58 atoms are connected to T12, T56, T66, T102 atoms,
T59 atom is connected to T56, T60, T83, T109 atoms,
T60 atoms are connected to T10, T30, T57, T59 atoms,
T61 atom is connected to T11, T53, T63, T64 atoms,
T62 atom is connected to T12, T28, T65, T94 atoms,
T63 atom is connected to T27, T51, T61, T99 atoms,
T64 atoms are connected to T61, T65, T93, T108 atoms,
T65 atoms are connected to T15, T35, T62, T64 atoms,
T66 atom is connected to T16, T58, T68, T69 atom,
T67 atom is connected to T17, T23, T70, T96 atoms,
T68 atoms are connected to T22, T56, T66, T100 atoms,
T69 atoms are connected to T66, T70, T95, T107 atoms,
T70 atom is connected to T20, T40, T67, T69 atom,
T71 atom is connected to T1, T43, T73, T74 atom,
T72 atom is connected to T2, T38, T75, T90 atom,
T73 atom is connected to T37, T41, T71, T97 atoms,
T74 atoms are connected to T71, T75, T89, T106 atoms,
T75 atoms are connected to T5, T25, T72, T74 atoms,
T76 atom is connected to T6, T48, T78, T79 atom,
T77 atom is connected to T7, T33, T80, T92 atoms,
T78 atoms are connected to T32, T46, T76, T98 atoms,
T79 atom is connected to T76, T80, T91, T105 atoms,
T80 atoms are connected to T10, T30, T77, T79 atoms,
T81 atom is connected to T4, T54, T89, T92 atoms,
T82 atom is connected to T2, T52, T91, T113 atoms,
T83 atom is connected to T9, T59, T90, T91 atoms,
T84 atoms are connected to T7, T57, T89, T114 atoms,
T85 atom is connected to T14, T44, T93, T96 atom,
T86 atoms are connected to T12, T42, T95, T115 atoms,
T87 atom is connected to T19, T49, T94, T95 atoms,
T88 atoms are connected to T17, T47, T93, T116 atoms,
T89 atoms are connected to T24, T74, T81, T84 atoms,
T90 atoms are connected to T22, T72, T83, T113 atoms,
T91 atom is connected to T29, T79, T82, T83 atoms,
T92 atoms are connected to T27, T77, T81, T114 atoms,
T93 atoms are connected to T34, T64, T85, T88 atoms,
T94 atoms are connected to T32, T62, T87, T115 atoms,
T95 atom is connected to T39, T69, T86, T87 atoms,
T96 atoms are connected to T37, T67, T85, T116 atoms,
T97 atom is connected to T3, T73, T103, T112 atoms,
T98 atoms are connected to T8, T78, T104, T111 atoms,
T99 atoms are connected to T13, T63, T101, T110 atoms,
T100 atoms are connected to T18, T68, T102, T109 atoms,
T101 atom is connected to T23, T53, T99, T108 atoms,
T102 atoms are connected to T28, T58, T100, T107 atoms,
T103 atom is connected to T33, T43, T97, T106 atoms,
T104 atoms are connected to T38, T48, T98, T105 atoms,
T105 atoms are connected to T9, T79, T104, T113 atoms,
T106 atoms are connected to T4, T74, T103, T114 atoms,
T107 atoms are connected to T19, T69, T102, T115 atoms,
T108 atoms are connected to T14, T64, T101, T116 atoms,
T109 atoms are connected to T29, T59, T100, T113 atoms,
T110 atoms are connected to T24, T54, T99, T114 atoms,
T111 atoms are connected to T39, T49, T98, T115 atoms,
T112 atoms are connected to T34, T44, T97, T116 atoms,
T113 atoms are connected to T82, T90, T105, T109 atoms,
T114 atoms are connected to T84, T92, T106, T110 atoms,
T115 atoms are connected to T86, T94, T107, T111 atoms,
T116 atoms are connected to T88, T96, T108, T112 atoms,
Borosilicate molecular sieve material . n is at least 10, X is a trivalent element (eg, includes one or more of B, Al, Fe, and Ga, eg, includes or is B), and Y is a tetravalent element A composition comprising a molar relationship of (n) YO ₂ : X ₂ O ₃ that is (eg, includes one or more of Si, Ge, Sn, Ti, and Zr, eg, includes Si or is Si). The borosilicate molecular sieve material according to claim 1 or 2, wherein: The borosilicate molecular sieve material according to claim 3, further comprising a noble metal and / or a salt of the noble metal. The as-synthesized form and the following peaks (d-interval (Å) / relative intensity (%)):
11.77-11.37 / 30-80,
9.51 to 9.11 / 20 to 70,
8.67-8.27 / 5-30,
5.64-5.44 / 10-40,
4.50-4.40 / 30-80,
4.28-4.18 / 30-80,
3.95-3.85 / 60-100, and
3.70-3.60 / 50-90
A borosilicate molecular sieve material having an X-ray diffraction pattern. 0.004 <m / n ≦ 0.04, n is at least 10, Q is an organic structure directing agent, X is a trivalent element (for example, one or more of B, Al, Fe and Ga) Including, for example, B or B, and Y includes one or more of tetravalent elements (for example, Si, Ge, Sn, Ti and Zr, for example, including Si, or is Si and _{which), mQ: (n) YO} 2: having a composition comprising the molar relationship X 2 _{O 3,} a borosilicate molecular sieve material according to claim 5. Q is represented by the following formula: R ₁ R ₂ (CH ₃ ) N ⁺ CH ₂ CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) R ₁ R ₂ , wherein R ₁ and R ₂ are independently butyl, Q is selected from pentyl and hexyl (eg, Q is N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane-1,4-diammonium, N, N ′ -Dihexyl-N, N'-dipentyl-N, N'-dimethylbutane-1,4-diammonium, N, N, N ', N'-tetrapentyl-N, N'-dimethylbutane-1,4- A cation selected from the group consisting of diammonium, N, N′-dipentyl-N, N′-dibutyl-N, N′-dimethylbutane-1,4-diammonium, and mixtures thereof). 6. The borosilicate molecular sieve material according to 6. A method for producing the borosilicate molecular sieve material according to any one of claims 1 to 7,
(I) preparing a synthetic mixture capable of forming the material, wherein the mixture comprises water, a hydroxide ion source, a tetravalent element Y oxide source, a trivalent element; A source of X, optionally a source of halide ions Z ⁻ , optionally a source of alkali metal ions M ⁺ , and N, N, N ′, N′-tetrahexyl-N, N′-dimethylbutane -1,4-diammonium cation, N, N′-dihexyl-N, N′-dipentyl-N, N′-dimethylbutane-1,4-diammonium cation, N, N, N ′, N′-tetra Pentyl-N, N′-dimethylbutane-1,4-diammonium cation, N, N′-dipentyl-N, N′-dibutyl-N, N′-dimethylbutane-1,4-diammonium cation and their Selected from the group consisting of mixtures Is comprise becomes a structure directing agent Q is and the synthetic mixture, with respect to the molar ratio, the following amounts and / or range: at least one _{YO 2 / X 2 O 3,} 5~60 of _H 2 O / YO ₂ , 0.01-1 OH ⁻ / YO ₂ , 0 −0.30 Z ⁻ / YO ₂ , 0.03 to 1.0 Q / YO ₂ , and 0 to 0.40 M ⁺ / YO _2. Having a composition of:
(Ii) heating the synthesis mixture at crystallization conditions comprising a temperature of about 100 ° C. to about 200 ° C. and a period of about 1 day to about 100 days until crystals of the material are formed; and (iii) Recovering the crystalline material from the synthesis mixture.   The method of claim 8, wherein the source of the trivalent element X is one or more of boric acid, sodium tetraborate, and potassium tetraborate.   10. A method according to claim 8 or 9, wherein the synthesis mixture has a pH of 8.0 to 10.5. It is the method of converting the raw material containing an organic compound into a conversion product, Comprising: The said raw material is an organic compound conversion condition, and / or in any one of Claims 8-10. Contacting with a catalyst comprising an active form of a borosilicate molecular sieve material produced according to the described method.

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